of basel



Na lw i in Patented Aug; 25, 1925- UNITED STATES rArEu'roFnc nnanann rnrrzscnn annraor. 'scnannnnnor BASE-L, swrrznnnn'nn, .essmnons TO socrm'r or cnmncan mnusrmz m BASLE, or nasnn, swrrznanmn.

. oranonrc m-rnnmnnm'rn rnonuc'rs Ann rnocnss or we sum. 7

i No Drawing.

To all whom it may concern:

Be it known that we, HERMANN Fm'rzsonn and PAUL SO AEDELI, both citizens of the Swiss Confederation, and residing at Basel, Switzerland, have inventcd'new and useful Cyanuric Intermediate Products and Processes of Making Same, of which the following is a full, clear, and exact specification.

The present invention. relates to new intermediate products. It comprises the new products as well as the process of makmgsame. a

It has been found that cyanuric halides may be condensed with a-naphthol to form new nucleal condensation products which a are valuable parent materials for the manufacture of dyestufis.

These new products are. obtained by the action of cyanurio halides which contain in the cyanuric ring at least one halogen atom which can. be exchanged and have the following general formulavv T f N A-d h-a N p (in which A and B also represent halogen atoms or any inorganic or organic residues,

capable of taking the place of halogen) on a-naphthol, preferably in presence of con de'nsin agents, such'as aluminum chloride or sul uric acid, in presence or absence of indifferent diluents, such as carbon bisul exchangeable halogen atoms in the cyanuric' nucleus, may be further condensed with compounds containing mobile hydrogen atoms, such as aminoand hydrox'y-com- Application filed nu aa, 192a Serial no. 721,530.

The new products, prepared according a3" i the herein described process, are most probably para-hydroxynaphthyl-l 3 5-triazines having the following general formula (in which A and B represent halogens, inorganic or organic residues capable of taking the place ofhalogens, such as aryl, OR,

'NHR (R meaningH alkyla l). I The new products form p;l e yellow yellow and rown powders, dissolving msulfuric acid to yellow, violet-blue and brown solutions, in caustic soda lye to yellow solutions; With acids th yi ld more or less stable salts having a; characteristi 7 color.

The following examples illustrate the invention. .7 V

' mEzamplc 1.

Into a melt of 58 parts of .a -naphthol at about C. is radually stirred a mixture of 18.5 parts 0 cyanuric chloride and 20 parts of aluminum chloride. "The reaction vsets in immediately, the temperature rising I and hydrogen chloride being evolved. After the mass has, been maintained at a temperature of 115 for a short time, it is almost solid. When ground after cooling, the product is a brick-red powder. After boili g 9o with much water containin hydrochl ric acid orange-red flocks are 0 tained, which appear to be the double compound of the condensation product fromone molecule of cyanuric chloride and three molecules of a-naphthol with one molecule of hydrochloric acid. For further purification they Y are dissolved in 1000 parts ofw'atier and Q0 '4 parts of concentrated caustic soda solution,

the-solution is filtered and theintensely yellow filtrate is treated with excess of hvdro:

i is of light yellow color. It dissolves in acetemperature atthc end of the" operation to of tetrachlorethane, while stirring.

chloric acidt'o l e-precipitate the co mpo'und.

Thecompound free from hydrochloric acid, namely 2': 4 6 tripara hydroxynaphthyl-- 1:3:.5-triazine,is obtained'by decomposing an alkaline solution of the'co'mpound by 3 means of a feeble acid, such as acetic acid or sodium bisulfite.

The 2': 4-: 6 triparahydroxynaphthyl- 1: 3:5-tri'azine of the following formula Example 2.

58 parts of a-naphthol are heated to 110 C. and the melt'thus obtained is mixed, in one portion, with 18.5 parts; of cyanuric chloride. After a short time reaction occurs with a lively elimination of hydrochloric acid, the temperature spontaneously rising to 140 C. Thereafter the mixture is heated for some time longer at160. C. untilno more hydrochloric acid is developed, and the product is isolated as described in Exam ple 1.

By adding a small quantity of sulfuric acid the'beginning of the reaction may be somewhat accelerated, it being of advanta e, in order to complete the reaction, to raise t e V QEasample 8. Y parts of a -naphthol-, 20 parts of alurninurnchloride and 1S 5 parts of cyannric chloride are added in succession to 200 parts mass gradually becomes heated to 60 C. and evolves hydrogen chloride. After it has been en'redissolyed in acetone, xylene tion and The warmed for-some hours on the'boiling water bath it is cooled, whereupon the condensation product. which has so aratedasa tou 'h mass, solidifies. It may 'e purified as escribed in Example 1 and is identical with the product of that examples Eaiomple 4. I 242 parts of the condensation product from one molecular proportion of cyanuric 7 chloride and'onemol'ecular proportion of aniline are mixed with 15 parts of aluminunichloride and the mixture is stirred into a melt of 45' parts of 'a-naphthol at C.

and the whole is heated for a short time to C. Thecooled mass is owdered, extracted by boiling water an dissolved in dilute caustic soda solution from which solution it is precipitated by hydrochloric acid. In this manner orange flocksare obtained which by dissolution in dilute caustic"""" soda solution and treatment with a feeble acid are converted into the Q-phenylamino- 4 26-di-para hydroxynaphthyl-l :3 :5-triazine in the form of feebly yellowish flocks.- 9 This triazine is a yellow powder when dried; it dissolves in concentrated sulfuric acid to abluish-red solution, from which on dilution with. water the product is preci ij tatcd again in the form of orange flocks. n 9 caustic alkali it is dissolved to an intensely.

yellow solution. When crystallized out-of acetone-xylene it melts at 255 258? C.

I v Ewample 5.

128 parts of the condensation product from one molecular proportion of cyanuric chloride and one molecular roportion' oi 'o-toluidine are introduced with 150 parts of a-naphthol into 1600 partsoftetrachlcrethane, while stirring vigorously, and treated with parts 'of aluminum chloride. Thereupon stirring is continued for some time at C. after which the 'mass is allowed to cool and the viscous prodmt of the reaction is separated from the diluent by decanting. -The product of reaction'is then boiled with dilute hydrochloric acid, wheret by it formsan orange-rcd powder which 15 filtered. dissolved in dilute caustic soda soluprecipitated by acidification with acetic acid. The 2-ortho-tolylamino4z 6-d1- para-hydroxynaphthyl-l 3: 5-triazine thus 120 :solution and in concentrated sulfuric acid. to ablmsh-rcd solution. In order to purify obtained-1:: bright yellow powder which dissolves in caustic soda solution to a yellow it completelycthe product is dissolved in ether and precipitated by means of gaseous.

hydrochloric acid. If recrystallized from a mixtureof acetone and xylene the new triazine softens at 190 C; and melts at about C.

The 2,(2-chloro)'- phenylamino 4: 6 di nu parahyd'roxyn-aphthyl 1 :3: fi-triazine obtained in an analogous manner from the condensation product from one molecular proportion of c'yanuricchloride, one molecular proportion of orthochloraniline (melting point 158 0.;1 andtwo molecular proportions of a-nap t (3.; the corresponding (2:5-dichloro).-compound obtainable from the condensation product from one molecular. proportion of cyanuric chloride and one molecular proportion of -22 51-dichlorai1iline v 170 C.) melts at about 155160 (3.; the

(melting point (4-chloro)-compound at about MiG-193 0.; and tam (3-nitro)-compound.at about 291- 292 Y I JEwa'mple 6. I Into a melt of 28 parts of a-naphthol at 90 C. is introduced, while stirring, a mixture of 14." parts ofc'hlorocyanuric diamide and 10 parts, of aluminum chloride. The

i melt is'heated to 120 C. for a short time, cooled, powdered and boiled with water conareintroduced 29.8 parts of the condensa-- tion product of melting point 196197 C; obtainable from one molecular proportion chloric acid.

taining' hydrochloric acid, whereby it is changed intoyellow flocks. These are filtered cold and separated from excess of a-naphthol by washing with acetone. There remains the yellow powder which is the hydrochloride of 2:4 diamino-6-para-hydrox-ynaphthyl-l :3: 5-triazine; it crystallizes from water containing hydrochloric acid in the form of slender yellow needles and when treated with sodium carbonate becomes the compound free from hydro- This triazine is almost colorless and melts at 305 308 C. It dissolves in alkalies to a feebly yellow solution and in concentrated sulphuric acid to an orange solution.

a E ma Into 28 parts of fiised cg-naphthol there of cyanuric chloride and two molecular proportions of aniline, and 10 parts of aluminu'm' chloride. After heaing for a short time to .C. the mass is powdered, extracted with boiling waterand then heated with about. 15 per cent of its weight of strong caustic soda solution. There se 'arates the sodium salt in the form 0 a smear mass which dissolves when diluted with 0t water. From this solution com- 'monsalt precipitates the sodium salt of: the

new condensation product. If 'it is dissolved in water and acetic acid is cautiously added, the 2 l-diphenylamino-ti-para-hy drox maphthyl-lzB:5 triazine is obtained whic by d ssolution in ether, addition 0 xylene to the solution and evaporation of ether, or by orystalliz ng from nitrobenzene,;may be further purified. It melts at hol melts at about 222225' 241 242'C., dissolves in concentrated sul- 55 furic acid to an orange solution, from which 6 it is precipitated in a yellow form by adding a little water, andin a by adding much water.

7 Example 8.

Into 1600 Parts f tetrachlorethane there f are introduced 111 parts of the secondary condensation product from one molecular proportion of cyanuric chloride, one molecular proportion of anline, and one molecu- 'lar proportion-of ammonia (white powder melting at 205-20.6 ,C.), together with 170 partsof ar-naphtholand 110. parts of aluminurn chloride, the whole being stirred for some time at C. The, product of the reaction is isolated as described in Example 7. The 2-phenylamino-4-amino-G-para-hy-..' drox'ynaphthyl-l:3:5-triazine forms a feebly yellowish powder which dissolves. in concentrated sulfuric acid to an orange solu' tion and in caustic soda solution to a bright yellow s'olution, melting, when recrystal- H lized from amixture of acetone and xylene,

at 238240. Q. 1 I

M Elaiomple 9.

Into 1600 parts of tetrachlorethane there are introduced, while cooling with ice, 51.2 parts of the condensation product from one molecular proportion of cyanuric chloride and one molecular proportion of o-tcluidine, together with 29 parts" of a-naphthol' and 51 parts of aluminum chloride. The mixture is stirred for some time, whereby the temperature gradually rises to 15 C.; the diluent is then distilled away with steam and the residue dried, dissolved in acetone and precipitated by introducing gaseous hydrochloric acid. The hydrochloric acid compound of the 2-chlorolrortho-tolylnmn no-fi-para-hydroxynaphthyl-l 3: 5 tria'zine. forms yellowishorange powder.

Example 10. Into 1000 parts of carbon bisuifide, cooled to 5 (3., there are introduced 93 parts of cyanuric chloride and then gradually 144 formed, is distilled away with steam. The

residue is dried and dissolved in acetone. 'l'he 2-chloro 4 6-d-i-para-hydroxynaphcolorless form I 2-chloro-4z'6-diaray- I thyl-l: 3:: -triazine in the form of a hydro- Treated with aluminum chloride and a- I naphthol it yields the 2:4:6-tri-para-hy-.

blown 0H with steam, the residue boiled with 'droxynaphthyl-l:3:5-triazine described in Example 1; heated with an excess of orthO- chloraniline it yields the 2 (Q-chloro) -phenylamino-4 6 di-para-l yrlroxynaphthyl-l 3 5- i triazine mentioned at the end of Example 5.

"Emma 11.

20.1 parts of the condensation product melting at 7' 778 C. from one molecular proportion of cyanunc chloride, one molemolecular proportion offannnonia are dissolved together with 17 parts of a -naphth'ol in 500 parts of tetrachlorethane'. After'additi on of 20 parts of aluminum chloride the mixture is heated for some hours, while stirring, to' 140 C; The solvent is then d lute hydrochloric acid, filtered and treated with caustic soda solution. The sodium salt of the 2-diethylamino-Lamino-G-para-hy droxynapthyl-l :3 :F-triazine is precipitated with common salt.- By dissolving the so-- diuin salt in water and precipitation with acetic acid there is obtained the free naphthol in form of bright yellow flocks whlch dissolve in'sulfuric acid to a brown-yellow solution. 4

What we claim is: r Y 1. The process for the manufacture of new intermediate products, consisting in reacting cyanuric compounds of the general formula:

halogen A. v A-l! Ln (wherein A and B represent halo ens or residues capable of taking the p ace of halogens) with mnaphthol,

2, The process for the manufacture of new intermediate products, consisting in reacting cyanuric compounds of the general formula: 1

(wherein A and B represent ha-lo ens or halogens) with a-naphthol in presence of a condensing agent.

I 3; The process for the manufacture of new intermediate products, consisting in re Q I 'ad (L3 (wherein it and Blrepresent halogens 01' residues capable of taking theplace of halogens), with a naphthol in presence of a conm 'densingjagent, and in condensing the prodcular proportion of dlethylamlne, and one ucts thus obtained further with compounds having mobile hydrogen atoms in amino acting cyan'uri'c compounds of the general formula &

(wherein A and represent halogens orresidues capable of taking the place of bald gens) with, anaphthol in presence of a con groups.

. 5. As new products the new compounds of the general formula:

(wherein and-B re resent halogens, inorganic or organ c resi ues capable '05 taking the place of halogens) which products f rm pale yellow to yellow and brown powders,

dissolving in sulfuric acid to yellow, bluish red, violet blue and .brown solutions, in.

caustic soda solution to "yellow to intensely yellow solutions, yielding with acids more or less stable salts having a chsracteristie 1 color. V y

6. As new roducts the new compounds of the general ormula:

(wherein A and. B represent inor anieor organic residues capable oftaking't e place of halogens) which products form pale yellow'to yellow and brown powders, dissolv- ,ing in sulfuric acid to yellow, b1uish-red,

violet-blue and brown solutions, in caustic soda solution to yellow to intensely yellow solutions, yielding with acids more orless stable salts haying a, characteristic color.

-7. As new products the new compounds of the general formula: 1

N .L-l} Ln pale yellow to yellow 'and brown powders, dissolving in sulfuric acid to yellow, bluish-red, violetblue and brown solutions, in caustic soda 1 up) I (wherein- A and B represent aromatic residues) which products form 

